Basic dyes



United States Patent 3,501,453 BASIC DYES Willy Steinemann, Basel, Switzerland, assignor to Sandoz Ltd. (also known as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Nov. 8, 1966, Ser. No. 592,712 Claims priority, application Switzerland, Nov. 12, 1965,

15,665/65; Feb. 8, 1966, 1,754/66 Int. C1. C09!) 29/02, 43/12; D06p 1/02 US. 'Cl. 260156 9 Claims ABSTRACT OF THE DISCLOSURE Pyridinium carbonamidobenzene azo (o-hydroxybenzene) dyes free from sulfonic acid groups yield dyeings with deep level shades having good light and Wetfastness when applied to acrylonitrile polymers.

This invention relates to basic dyes free from subphonic acid groups and a process for the production of these dyes. The have the formula R stands for hydrogen or a substituted .or unsubstituted alkyl, cycloalkyl or aralkyl radical,

R stands for hydrogen or a substituted or unsubstituted alkyl radical, each of the radicals R and R stands for hydrogen, halogen or a substituted or unsubstituted alkyl or alkoxy radical,

R stands for hydrogen or a non-water-solubilising substituent, preferably a substituted or unsubstituted alkyl or alkoXy radical,

R stands for hydrogen, halogen, nitro or a substituted or substituted alkyl or alkoxy radical and A stands for an anion equivalent to the dye cation, and

in which the ring D may be further substituted.

The new dyes of Formula I can be obtained by condensing a compound of the formula with a carboxylic acid of the formula ZCOOH (III) or with one of its functional derivatives, for example an acid halide, such as an acid chloride or bromide, wherein Z represents a radical of the formula 3,501,453 Patented Mar. 17, 1970 When Z is a radical of Formula V, a compound of the formula is added on to the reaction product.

Certain of these dyes, for example those of the formula where R represents a substituted or unsubstituted alkyl or alkoxy radicals, can be obtained by coupling the diazo component of an amine of the formula I B COI|\I D -NH2 9 N/ R2 RFI 9 R1 (VIII) with a coupling component of the formula R9 (IX) The dyes of Formula I can also be produced by coupling the diazo compound of an amine of the formula OH Ra I 1 R7 with a coupling component of the formula R2 (XI) and treating the resulting compound of Formula II with a carboxylic acid of Formula III or with one of the functional derivatives of such an acid to convert it into a dye of Formula I.

Particularly good dyes are those corresponding to the formula in which the ring-D is substituted by halogen or by alkyl or alkoxy which may be further substituted, those of the formula R6 OH s B COlTI--N=N E 9 B2 R6 IIIG3 R7 J in which the ring E bears at least one alkoxy group, and those of the formula R represents a substituted or unsubstituted alkyl or alkoxy radical, and R halogen or a substituted or unsubstituted alkyl or alkoxy radical.

The azo coupling reaction can be effected in the known Way in an alkaline to acid medium which may be buffered if necessary.

The condensation reaction can be carried out in an organic solvent in the presence of an acid or water acceptor, as required, and at high temperatures, for example at to 150 C. or preferably 70 to 120 C. It is possible to work without solvent when one of the compounds can be employed in the liquid state; in such cases this particular reactant is best employed in excess.

The ring D may be substituted by halogen or by alkyl or alkoxy which may be further substiuted.

The anion A may be an organic or inorganic ion, for example a halogen ion, such as chloride, bromide and iodide; methyl sulphate; sulphate; disulphate; perchlorate; phosphorus tungsten molybdate; benzene sulphonate; 4-chlorbenzene sulphonate; oxalate; maleinate; acetate; propionate; methanesulphonate; chloroacetate or benzoate; or a complex anion, such as those of zinc chloride double salts.

Examples of suitable compounds of Formula VI are alkylating or quaternating agents, e.g. the esters of strong mineral acids and organic sulphonic acids, such as alkylchlorides, alkylbromides, alkyliodides or alkylsulphates, e.g. methyliodide, -bromide or -chloride, dimethylsulphate, aralkyl halides, the esters of lower alkanesulphonic acids which may be int-halogenated, such as the alkyl esters of methane-, ethaneor butane-sulphonic acids, the esters of benzene-sulphonic acids which may be further substituted, such as the methyl, ethyl, propyl or n-butyl esters of benzene-sulphonic acid, 2- or 4-methylbenzene sulphonic acid, 4-chlorobenzenesulphonic acid or 3- or 4-nitrobenzenesulphonic acid. The addition reaction, i.e. the quaternation or alkylation, is carried out preferably in an inert solvent or if suitable in aqueous suspension, or without solvent in an excess of the alkylating agent at temperatures above 10 C. The medium may be buffered if necessary.

The dyes thus formed can be isolated by standard methods, such as evaporation, precipitation, distillation, filtration, decantation, etc. If necessary they are purified, but if already of sufficient purity they are used as obtained.

Examples of suitable alkyl radicals which may bear 1 to 12 or preferably 1 to 6 carbon atoms and may be substituted are methyl, ethyl, propyl, tert. butyl, tert. a'myl, hydroxyethyl, chloroethyl and cyanoethyl. Examples of suitable alkoxy radicals which may contain 1 to 6 or preferably 1 to 4 carbon atoms and may be substituted are methoxy, ethoxy, and butoxy. Halogen may be chlorine, bromine or fluorine. The cycloalkyl radical represents preferably a cyclohexyl radical; the aralkyl radical may be, for example, a benzyl radical.

In Example 10 of German application No. 1,044,023, which has been placed open to public inspection, a process is described for dyeing polyacrylonitrile fibres with dyes including a basic dye of the formula 4 In this specification it is stated that phenol or 2-naphthol can be used in place of pyrazolone as coupling component for the formation of the aforenamed dye.

It is known from French Patent No. 1,257,255, Example 1, that polyacrylonitrile fibres can be dyed with the dye of the following formula The dyes of Formula I have better levelling properties than the aforecited dyes, give dyeings of greater depth and higher light fastness, and can be applied within a Wider pH range. They are used preferably for dyeing, padding or printing filaments, fibres or textile materials of polyacrylonitrile or acrylonitrile copolymer fibers, on which they give deep, level shades having good fastness to light and wet treatments, especially washing, water, seawater, perspiration, decatising, cross dyeing, dry cleaning and solvents, and good resistance to heat, sublimation, ironing and pleating. They show good compatibility With salt and are well soluble, particularly in water.

Acrylonitrile copolymer fibres generally consist of to acrylonitrile and 20 to 5% vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester etc.

These fibres can be dyed in blends with others. Dyeing is generally carried out in an aqueous medium of alkaline, neutral or acid reaction at 80 to C. or preferably at the boil, or at temperatures above 100 C. with pressure. At these temperatures very level dyeing are obtained without the assistance of retarders. Blend fabrics containing a polyacrylonitrile fibre component can be successively dyed with the dyes of the present invention. They are also suitable for the mass dyeing of polyacrylonitrile in lightand wet-fast shades and for the coloration of oils, paint media, plastic moulding compounds, spinning solution of fibre-forming materials, and polyesters or A solution of 25.7 parts of 4-:amino-2-methyl-2'-hydroxy-5-methoxy-1,1'-azobenzene in 220 parts of chlorobenzene is raised to 100 and at this temperature nicotinyl chloride is dropped in over a period of 2 hours to acylate the amino group of the aminoazo dye.

On completion of acylation, 25 parts of dimethylsulphate are added over 30 minutes, and the mixture is then boiled for 1 hour with reflux. On cooling, the quaternary dye which has the formula I -oo-HN N=N ornsoi e I CH3 6 is collected on a filter and if necessary is purified by renicotinic acid chloride in 200 parts of toluene at 80-90". crystallisation from aqueous solution. It dyes polyacrylo- Stirring is continued for 1 hour, after which time 27.3 nitrile fibres in greenish yellow shade of good levelness parts of 4-amino-2,5-dimethoxy-2'-hydroxy-1,1-azobenand excellent fastness. The shade of the dyein-gs is pH- zene in fine powder form are added at 80-90". The reacstable. tion temperature is increased to 108 and this temperature maintained until the development of hydrogen chloride has ceased. On cooling, the precipitated dye is collected on a filter and purified by recrystallization from raised to 95 and after 20 minutes at this temperature Water' It yellow dyeings of excellent fastness on 5 parts of 1 methy1pyridinium 3 carboxylic polyacrylonitrile fibres, which are very level and show nitranilidemethylsulphate are added. After a further Very good stablllty t0 P Changesminutes at 95 the suspension is adjusted with sodium The mode of Operation described in Example 1 can carbonate to give a marked alkaline reaction to phenolemployed for the production of cationic dyes of similar phthalein. The reduction solution is filtered free of the structure using the diazo, azo and acylating components iron scum and the clean filtrate cooled to 0. It is diazo- 15 listed in the following Table A.

EXAMPLE 2 15 parts of fine cast-iron chips are suspended in 100 parts of 1% acetic acid by stirring. The suspension is TABLE A Shade of dyeing on polyacrylo- Diazo component Azo component Acylating component nitrile fibres Example:

4 2-amino-1-hydroxy-4-chlorobenzene 1-amino-2-methoxy-5methylbenzene Nieotinyl chloride Yellow. 2-amino-l-hydroxy-4 methylbenz ene do do Do. 2-amino-l-hydroxy-benzene do Picolinic acid ehloride Do. l-amino-2-hydroxy4-nitrobenzene ,5-dimethylbenzen do Red-yellow. 2-amino-l-hydroxy-benzene 1-amino-3-mcthoxy-benzene Isonicotinic acid chlorid Yellow.

2'amino-1-hydroxy-4-nitrobenzene l-amino-3-methyl-benzene do Do.

tised with 3.3 parts of sodium nitrite and 30% hydro- Employing the mode of operation of Example 2, catchloric acid at 0 to 5 in the normal way and the diazo ionic dyes of similar structure can be obtained with the compound is coupled with 6 parts of 1-hydroxy-4 methyl- 30 diazo and coupling components l sted in the following benzene in 80 parts of water in the presence of sodium Table B.

TABLE B Shade of dyeing on polyaciylo- Example Diazo component; Coupling component nitrile fibres Methyl sulphate oi 4-amino-l-methyl-pyridinium-3-carboxylic acid anilide l-hydroxy-2,4-dimethylbenzene Yellow. Methlyllsulphate oi 4-aminc-1,3-dimethyl-pyridinium-3-carboxylic-acid l-hydroxy-3,4dimethylbenzene Do.

am i e. Methyl sulphate of 4-amino-3-chloro-l-methylpyridinium-3-carboxylic acid -.d0 Do.

an 1 e. 13- Methlyllsulphate of 4-amino-1,2,5-trimethyIpryidinum-Ii-carboxylic acid l-hydroxy-2,4-dimethylbenzene Do.

am 1 e. 14 do 1-hydr0xy-4-methoxybenzene Reddish yellow. 15.. do l-hydroxy--tert. butylbenzene-.. Yellow. 16 Methyl sulphate of 4-amino-l-methyl-pyridinium-Z-carbcxylic acid anilide l-hydroxy-2,4-dimethoxybutyl Orange. 17 Methyl sulphate of 4-amino-l-methyl-pyridiniumA-carboxylic acid anilide l-hydroxyA-ethoxybenzene Reddish yellow. 18 Chlorohydrate oi 4-amino-1-n1ethyl-pyridinium-4-carboxylic acid anilide l-hydroxy-3,4-dimethylbenzene- Yellow. 19 o .4 1-hydroxy-4-te1-t amylbenzene.-. Do. 20. do 1 hydroxy-2,4-diethoxybenzene--. Reddish yellow. 21- Methyl sulphate of 4-amino-l-methyl-pyridinium-2-carboxylic acid anilide- 1-hydroxy-3,4-dimethylbenzene Yellow. 22.. do l-hydroxy-2-methoxy-4-methylbenzene. Reddish yellow. 22a Methyl sulphate oi 4-amino-1-methyl-pyridinium-3-carboxylic acid anilide 1 hydroxy-3,4-dimethylbenzene Yellow.

carbonate at 015 and pH 9.0-9.5. When the coupling The mode of operation described in Example 3 can be reaction is complete, the pH of the solution is adjusted 50 employed to produce cationic dyestuffs of similar structo 1.0-2.0 by dropping in 30% hydrochloric acid. It is ture using the amino-azo-benzene derivatives and acylating then raised to 45 and held at this temperature for 15 components set out in the following Table C.

TABLE 0 Shade of dyeing on polyacrylo- Example 4amino-aZo-benZene derivative Acylating component nitrile fibres 23 4-amino-2-hydroxy 1-methylpyridinium-B-carboxylic acid chloride-methyl sulphate Yellow.

3-methoxy-5-methyl-1,1-azohenzene. 24 4-amino-2-hydroxy-3,5 dimethyl-1,1-azobenzene .d0 25 do l-methylpyridinium Z-carboxylic acid chloride-methyl sulphate Do. 26 4-amino-2-hydroxy ..do Reddish yellow.

3-methoxy-5'-methyl-1,1'-azobenzene. 27 4-amino-2-hydroxy-3-chloro-5-methy1-1,1- do Yellow.

azobenzene. 28 do 1-methylpyridiniumt-carboxylic acid chloride-methyl sulphate Do. 29 4-amino-2-hydroxy 5-methoxy-1,l-azobenzene.. do Reddish yellow 30 4-amino-2-hydroxy do Orange.

2,5-dimethoxy-4'-tert. butyl-1,1-azobenzene.

minutes. On cooling, the precipitated yellow dye is fil- APPLICATION EXAMPLE A ff fi fif 123? $311??? $315225? 5123 ii ifflifiliiii PM of the dye Obtained in with 0 m q y p y W ample 1 and 80 parts of dextrin are intimately mixed in fibres in greenish yellow shades of excellent levelness and 70 a ball mill f0 r minutes. One art of the res lt1 m xhigh light and wet fastness. The shade of the dyemgs 1s ture is pasted with 1 part of 8 acetic aci 6 pains EXAMPLE 3 of distilled water at are run onto the paste with constant stirring and the solution is boiled for a short time. 14.5 parts of dimethyl sulphate are added dropwise in It is diluted wtih 7600 parts of distilled water, and 2 parts the course of 30 minutes to a solution of 16.4 parts of of glacial acetic acid are added. parts of polyacrylonitrile fibre are entered into this dyebath at 60, following a preliminary treatment of 10-15 minutes at 60 in a bath of 8000 parts of water and 2 parts of acetic acid. The dyebath is raised to the boil in minutes and held at the boil for 1 hour. A level greenish yellow dyeing is obtained on the polyacrylonitrile fibre which has excellent light and good wet fastness properties.

'EXAMPL'E 31 of chlorobenzene at 100. 1n the course of 1 hour 26.2 parts of dimethyl sulphate are added to the dye solution at 100, after which the reaction mixture is bo led for 2 hours with reflux. The precipitated quaternary dye is filtered oif, purified by recrystallisation from aqueous solution, dried and ground. It dissolves in water to give yellow-brown solutions and is suitable for dyeing polyacrylonitrile fibres in reddish yellow shades, which have excellent light and wet fastness properties.

Equally good dyes are obtained when the 12.4 parts of 1-hydroxy-4-methoxybenzene used in this Example are replaced by equimolar amounts of 1-hydroxy-2-methoxy- 4-methylbenzene, 1-hydroxy-4-ethoxybenzene, l-hydroxy- 3,4-dimethylbenzene, 1-hydroxy-2,4-dimethylbenzene or 1-hydroxy-4-methylbenzene.

Cationic dyes of similar structure can be produced by the method described in Example 31 with the diazo, azo, acylating and quaternating components listed in the following Table D.

TABLE D Shade of dyeing Example on polyaerylo- No. Diazo component Azo component Acylating component Quaternating component nitrile fibres 33 1-aJ11ino-2-hydroxy- 1-methylamino-3-methyl- Pyridine-B-earboxylie acid (OHmSOi Yellow. benzene. benzene. chloride. 34 do 1-methylamino-2,5- d0 (CHmSQ, Do.

dimethylbenzenc.

35 1-amino-2-hydroxy-5- do d0 OHa- SO CH Do.

methylbenzene.

36 .-do 1-ethylamino-3-methyl- ..d0 CH SO OH Do.

benzene.

37 do do Pylidine-z-carboxylic acid CH SO CH Do.

chloride.

dodo Pyridine4-carboxylic acid IIO4HQBI Do, chloride. 39 l-amino-Z-hydroxydo .-do nC H Br Do.

benzene.

40 d0 .-do Pyridine-2-earboxylic acid CH 40 0,11. Do.

' chloride.

41 l-amino-Z-hydroxy- 1-benzy1amin0-3-methy1- -d0 (01102804 Yellow.

benzene. benzene. l 42 do .do Pyr1d1ne-3-earboxylic acid (CHmSO Do,

chloride. 43 do ..do Py i iingi-carboxylic acid (oHmso. Do.

0 on 44 do l-ethylamino-Z-methoxy- Pyridine-Ii-carboxylic acid nC H Br 13 benzene. chloride. l-amino-Z-hydroxyl-methylamino-2-m h- ..--.do 011 604); Do.

benzene. oxy-fi-methylbenzene. 4 do 1-ethylamino-3-methoxydo onnson, D0.

benzene. 47 1-amino-2-hydroxy-5- .d0 0 0113(804): Reddlsh yellow.

methoxybenzene.

4s do 1-ethylamino-3-methyl- ..do 011 30 011 Do,

benzene.

49 do l-methylaminodaneth- .-do G4H9B1 D oxybenzene. 50 1-amino-2-hydroxy-5- .do .d0 (CH3)2S04 Do.

tert.-butylbenzene. 51 do 1-methylammo-2-methyl- Pyridme-ii-carboxylic acid (0119280 Yellow benzene. chloride. 52 do l-methylaminob-Inethyldo (GHmsm Do,

benzene.

the free base by stirring in a 2% sodium carbonate solu- Formulae of representative dyes of the foregoing examtion at 20. The dried nicotinic acid amide dye is disples are as follows:

solved in 250 parts of toluene at 90, and 12.6 parts of dimethyl sulphate are added to the solution in the course of 1 hour. The precipitated quaternary dye is filtered 01f, recrystallised from aqueous solution and dried. It dyes polyacrylonitrile fibres in greenish yellow shades of excellent levelness and fastness; the dyeings of this dye are pH-stable.

EXAMPLE 32 22.7 parts of pyridine 3 carboxylic acid N- methyl-N' (4" aminophenyl) amide are diazotised at 0-5 in aqueous hydrochloric acid solution. The diazo solution is coupled in the normal way with 12.4 parts of 1-hydroxy-4-methoxybenzene in soda-alkaline solution at 020. On completion of coupling, the dye is isolated in the normal way, vacuum dried and dissolved in 600 parts 3, 501,453 9 10 EXAMPLE 6 from the group consisting of hydrogen, halo, alkyl, substituted alkyl, alkoxy and substituted alkoxy; R is a member selected from the group consisting of hydrogen, alkyl substituted alkyl, alkoXy, substituted 9 alkoxy, chloro and nitro; 01 R is a member selected from the group consisting of I G CH3 The basic dye of formula hydrogen, halo, nitro, alkyl, substituted alkyl, alkoxy and substituted alkoXy; A is an anion equivalent to the dye cation; and EXAMPLE 7 10 any ring D substituent is a member selected from the f f 1 group consisting of halo, alkyl, alkoxy, substituted alkyl The baslc dye o Ormu a and substituted alkoxy; and in each of the above defini- OH tions each alkyl has from 1 to 12 carbon atoms; each I 6 alkoxy has from 1 to 6 carbon atoms; and any unde- CO NHT CH3 Cl 15 fined substituent is a member selected from the group consisting of hydroXy, chloro, methoxy and cyano.

a 2. A basic dye according to claim 1 wherein ring D is substituted by a member selected from the group con- EXAMPLE 8 sisting of halo, alkyl and alkoxy. The baslc dye of formula 3. A basic dye according to claim 1 wherein at least one of R and R is alkoxy.

(I3ZH5 4. A basic dye according to claim 1 wherein R is a -CONN=N CH3S04 member selected from the group consisting of alkyl, sub- Ng' I stituted alkyl, alkoxy and substituted alkoxy; and R is a l on J member selected from the group consisting of halo, alkyl,

a substituted alkyl, alkoxy and substituted 'alkoxy.

EXAMPLE 9 5. The basic dye according to claim 1 of the formula The basic dye of formula 0 CH3 (I311 OH F CH3 CONH N=N@ 011E04 CO-I1I-N=N 011E04 f? 1 i 00H CH3 3 H3 3 6. The basic dye of the formula EXAMPLE 22a 0H Oo NH @LN=N -CONHN=N 0113 01 f? N5- CH3 CH3 I ([3113 Ch 7. The basic dye of the formula EXAMPLE 31 F on P t CH3 3 N6B & 4

H3 H3 8. The basic dye of the formula EXAMPLE 32 02H5 1 on OOl I-N=N 0113504 (3H3 CO-N--N=N CH3SO49 (13H: hm

(IJH: C 9. The basic dye of the formula I F OH Having thus disclosed the invention, what I claim is: I 1. A basic dye free from sulfonic acid groups and of CO-NN=N CH3SO4 the formula l 5 0011, R6 OH 3 References Cited B F D A9 UNITED STATES PATENTS al R2 1'1, 2,365,265 12/1944 Gross 260156 Rl 2,821,526 1/1958 Boyd 260156 XR 3,117,960 1/1964 Illy 260-156 wherein: 3,148,181 9/1964 Wallace et al. 260--l56 XR R is a member selected from the group consisting of 7 3,312,681 4/1967 Lewls 260- 156 hydrogen, alkyl, cyclohexyl, benzyl, substituted alkyl, substituted cyclohexyl and substituted benzyl; FLOYD HIGEL Pnmary Exammer R is a member selected from the group consisting of U S C1 XR hydrogen, benzyl alkyl and substituted alkyl; each of R and R is, independently, a member selected 260-295, 146, 142, 205, 295.5; 841, 71 

